Protective film material for biosensor probe

Abstract

The present disclosure provides, as a film structure useful for a probe of a biosensor, a film structure comprising a detection layer including an analyte-responsive enzyme; and a protection film formed on the detection layer, in which the protection film includes alone poly(styrene-ran-4-vinylpyridine-ran-propyleneglycol methacrylate); or the protection film includes a copolymer mixture including poly(styrene-ran-4-vinylpyridine-ran-propyleneglycol methacrylate); and poly(4-vinylpyridine)-block-poly(C1-15 alkyl methacrylate), or poly(4-vinylpyridine-ran-2-hydroxyethyl methacrylate).

1 - 5 . (canceled) 
     
     
         6 . A protection film used in a probe for a biosensor, the protection film comprising poly(styrene-ran-4-vinylpyridine-ran-propyleneglycol methacrylate) represented by Formula (1): 
       
         
           
           
               
               
           
         
         where m represents an integer of 1 to 20; x, y, and z each represent mole fractions of three types of monomer units of styrene, 4-vinylpyridine, and propyleneglycol methacrylate, and satisfy a relationship x+y+z=100; and w represents a number average molecular weight. 
       
     
     
         7 . A protection film used in a probe for a biosensor, the protection film comprising a copolymer mixture including:
 poly(styrene-ran-4-vinylpyridine-ran-propyleneglycol methacrylate) represented by Formula (1):   
       
         
           
           
               
               
           
         
         where m represents an integer of 1 to 20; x, y, and z each represent mole fractions of three types of monomer units of styrene, 4-vinylpyridine, and propyleneglycol methacrylate, and satisfy a relationship x+y+z=100; and w represents a number average molecular weight; and 
         poly(4-vinylpyridine)-block-poly(C 1-15  alkyl methacrylate) represented by Formula (2): 
       
       
         
           
           
               
               
           
         
         where R represents an alkyl group having 1 to 15 carbon atoms; p and q each represent repeating units of two types of monomer units of 4-vinylpyridine and C 1-15  alkyl methacrylate; and w represents a number average molecular weight; or poly(4-vinylpyridine-ran-2-hydroxyethyl methacrylate) represented by Formula (3): 
       
       
         
           
           
               
               
           
         
         where s and t each represent mole fractions of two types of monomer units of 4-vinylpyridine and 2-hydroxyethyl methacrylate, and satisfy a relationship s+t=100; and w represents a number average molecular weight. 
       
     
     
         8 . The protection film according to  claim 6 , wherein in Formula (1) the mole fraction x of styrene is 5 to 30% and a relationship of the mole fraction x of styrene, the mole fraction of y 4-vinylpyridine, and the mole fraction z of propyleneglycol methacrylate is x+y+z=100. 
     
     
         9 . The protection film according to  claim 8 , wherein in Formula (1) the mole fraction x of styrene is 10 to 30%. 
     
     
         10 . The protection film according to  claim 9 , wherein in Formula (1) the mole fraction x of styrene is 5 to 25%. 
     
     
         11 . The protection film according to  claim 6 , wherein in Formula (1) the mole fraction y of 4-vinylpyridine is 45 to 60% and a relationship of the mole fraction x of styrene, the mole fraction y of 4-vinylpyridine, and the mole fraction z of propyleneglycol methacrylate is x+y+z=100. 
     
     
         12 . The protection film according to  claim 9 , wherein in Formula (1) the mole fraction y of 4-vinylpyridine is 50 to 60%. 
     
     
         13 . The protection film according to  claim 6 , wherein in Formula (1) the mole fraction z of propyleneglycol methacrylate is 15 to 30% and a relationship of the mole fraction x of styrene, the mole fraction y of 4-vinylpyridine, and the mole fraction z of propyleneglycol methacrylate is x+y+z=100. 
     
     
         14 . The protection film according to  claim 9 , wherein in Formula (1) the mole fraction x of propyleneglycol methacrylate is 20 to 25%. 
     
     
         15 . The protection film according to  claim 6 , wherein the number average molecular weight of the polymer represented by Formula (1) is 40 to 80×10 3 . 
     
     
         16 . The protection film according to  claim 6 , wherein the number average molecular weight of the polymer represented by Formula (1) is 45 to 60×10 3 . 
     
     
         17 . The film structure according to  claim 6 , wherein the protection film further includes poly(2-methoxyethylacrylate). 
     
     
         18 . The protection film according to  claim 7 , wherein in Formula (1) the mole fraction x of styrene is 5 to 30% and a relationship of the mole fraction x of styrene, the mole fraction of y 4-vinylpyridine, and the mole fraction z of propyleneglycol methacrylate is x+y+z=100. 
     
     
         19 . The protection film according to  claim 18 , wherein in Formula (1) the mole fraction x of styrene is 10 to 30%. 
     
     
         20 . The protection film according to  claim 19 , wherein in Formula (1) the mole fraction x of styrene is 5 to 25%. 
     
     
         21 . The protection film according to  claim 7 , wherein in Formula (1) the mole fraction y of 4-vinylpyridine is 45 to 60% and a relationship of the mole fraction x of styrene, the mole fraction y of 4-vinylpyridine, and the mole fraction z of propyleneglycol methacrylate is x+y+z=100. 
     
     
         22 . The protection film according to  claim 19 , wherein in Formula (1) the mole fraction y of 4-vinylpyridine is 50 to 60%. 
     
     
         23 . The protection film according to  claim 7 , wherein in Formula (1) the mole fraction z of propyleneglycol methacrylate is 15 to 30% and a relationship of the mole fraction x of styrene, the mole fraction y of 4-vinylpyridine, and the mole fraction z of propyleneglycol methacrylate is x+y+z=100. 
     
     
         24 . The protection film according to  claim 19 , wherein in Formula (1) the mole fraction x of propyleneglycol methacrylate is 20 to 25%. 
     
     
         25 . The protection film according to  claim 7 , wherein the number average molecular weight of the polymer represented by Formula (1) is 40 to 80×10 3 . 
     
     
         26 . The protection film according to  claim 7 , wherein the number average molecular weight of the polymer represented by Formula (1) is 45 to 60×10 3 . 
     
     
         27 . The protection film according to  claim 7 , wherein the number average molecular weight of each block constituting the polymer represented by Formula (2) is 50 to 200×10 3 . 
     
     
         28 . The protection film according to  claim 7 , wherein the number average molecular weight of each block constituting the polymer represented by Formula (2) is 65 to 100×10 3 . 
     
     
         29 . The protection film according to  claim 7 , wherein in Formula (3) the mole fraction s of 4-vinylpyridine is 40 to 80, and a relationship of the mole fraction s of 4-vinylpyridine, and the mole fraction t of 2-hydroxyethyl methacrylate is s+t=100. 
     
     
         30 . The protection film according to  claim 29 , wherein in Formula (3) the mole fraction s of 4-vinylpyridine is 60 to 70. 
     
     
         31 . The protection film according to  claim 7 , wherein in Formula (3) the mole fraction t of 4-vinylpyridine is 20 to 60, and a relationship of the mole fraction s of 4-vinylpyridine, and the mole fraction t of 2-hydroxyethyl methacrylate is s+t=100. 
     
     
         32 . The protection film according to  claim 31 , wherein in Formula (3) the mole fraction t of 2-hydroxyethyl methacrylate is 30 to 40. 
     
     
         33 . The protection film according to  claim 29 , wherein in Formula (3) the mole fraction t of 4-vinylpyridine is 20 to 60, and a relationship of the mole fraction s of 4-vinylpyridine, and the mole fraction t of 2-hydroxyethyl methacrylate is s+t=100. 
     
     
         34 . The protection film according to  claim 33 , wherein in Formula (3) the mole fraction t of 2-hydroxyethyl methacrylate is 30 to 40. 
     
     
         35 . The protection film according to  claim 30 , wherein in Formula (3) the mole fraction t of 4-vinylpyridine is 20 to 60, and a relationship of the mole fraction s of 4-vinylpyridine, and the mole fraction t of 2-hydroxyethyl methacrylate is s+t=100. 
     
     
         36 . The protection film according to  claim 35 , wherein in Formula (3) the mole fraction t of 2-hydroxyethyl methacrylate is 30 to 40. 
     
     
         37 . The film structure according to  claim 7 , wherein the protection film further includes poly(2-methoxyethylacrylate). 
     
     
         38 . A probe for a biosensor, the probe comprising:
 a working electrode;   a reference electrode; and   a counter electrode;   a detection layer formed on the working electrode; and   a protection film covering the working electrode,   wherein   the detection layer includes an analyte-responsive enzyme and a redox mediator; and   the protection film includes poly(styrene-ran-4-vinylpyridine-ran-propyleneglycol methacrylate) represented by Formula (1):   
       
         
           
           
               
               
           
         
         where m represents an integer of 1 to 20; x, y, and z each represent mole fractions of three types of monomer units of styrene, 4-vinylpyridine, and propyleneglycol methacrylate, and satisfy the relationship x+y+z=100; and w represents a number average molecular weight. 
       
     
     
         39 . A probe for a biosensor, the probe comprising:
 a working electrode;   a reference electrode; and   a counter electrode;   a detection layer formed on the working electrode; and   a protection film covering the working electrode,   wherein   the detection layer includes an analyte-responsive enzyme and a redox mediator; and   the protection film includes a copolymer mixture including:   poly(styrene-ran-4-vinylpyridine-ran-propyleneglycol methacrylate) represented by Formula (1):   
       
         
           
           
               
               
           
         
         where m represents an integer of 1 to 20; x, y, and z each represent mole fractions of three types of monomer units of styrene, 4-vinylpyridine, and propyleneglycol methacrylate, and satisfy a relationship x+y+z=100; and w represents a number average molecular weight; and 
         poly(4-vinylpyridine)-block-poly(C 1-15  alkyl methacrylate) represented by Formula (2): 
       
       
         
           
           
               
               
           
         
         where R represents an alkyl group having 1 to 15 carbon atoms; p and q each represent repeating units of two types of monomer units of 4-vinylpyridine and C 1-15  alkyl methacrylate; and w represents a number average molecular weight; or 
         poly(4-vinylpyridine-ran-2-hydroxyethyl methacrylate) represented by Formula (3): 
       
       
         
           
           
               
               
           
         
         where s and t each represent mole fractions of two types of monomer units of 4-vinylpyridine and 2-hydroxyethyl methacrylate, and satisfy a relationship s+t=100; and w represents a number average molecular weight.